Plastic condensation products from orthocresol



' UNITED srA'rEs PATENT .QFFICE.

LEO 3:. am or 'YonxEns, NEW YORK.

rmsrrc connnnsarron rnonuc'rs mom onrnocnnson No Drawing.

To all whom it may concern:

Be it known that I, Lno H. BAEKELAND, a citizen of the United States, residing at Yonkers, in the county of-Westchester and State of New York,-have invented certain new and useful Improvements in Plastic Condensation Products from Orthocresol, of which the followin is a specification.

In my United tates Patents Numbers 1,088,677 and 1,088,678 I have disclosed the possibility of increasing the strength and resistivity of condensation. products .pre-

pared from cresol and methylene-containing.

bodies by-insuring in the mixtures used a preponderance of meta-cresol, which of the three isomeric cresols reacts most readily with formaldehyde or its equivalents, and

tends to form condensation products of,

which the infusibility and general. resistance to chemicals and solvents is highest.

. Such use of meta-cresol or of cresol mixtures enriched in meta-cresol constitutes adirect advantage in any case where such properties are mostly desired.

A careful study of the relative behavior of the three isomers, meta-cresol, orthocresol, and para-cresol, has shown that orthoand 'ara-cresol when treated with fgrmaldehyd or its equivalents containing a mobile methylene group (hexamethylenetetramine, etc.) according to known methods have a tendency to yield products. of the socalled permanently fusible and soluble class, known also as the saliretin-resin or saliretin class. There are however some conditions under which products of the infusibleclass are formed. For instance, infusible products are obtained when para-cresol reacts upon formaldehyde present in suflicient roportions, provided caustic soda is use as the condensing agent. If, however, hydrochloric acid isused as a condensingagent the roduct is more. or less fusible and britt e, being similarin this respect to the saliretins, or resins of the Novolak type, even when relatively large proportions of formaldehyde are used; that'is to say, such proportions as in the case of henol or metacresol would produce decide y hard and infusible products.

Ortho cresol, although less a t to yield infusible products thanphenol oxybenzol) or meta-cresol, can under certain conditions be made to yield infusible condensation v Specification of Letters Patent.

Application filed May 10, 1918. Serial No. 233,808.

Patented Jan. 3-, 1922.

products; but in general this requires higher temperatures and decidedly longer heating than when meta-cresol or henol is used under the same conditions. nfusible products are however readily obtained from ortho-cresol and suflicient formaldehyde or its equivalents under certain conditions as described below, especially when basic condensmg agents, including the. fixed alkalies, are used. I I

The results are therefore distinctly differentiated from those described in the patents of Farbenfabriken vorm. Friedr. Bayer & Co. (German Patent No. 201,261 and Brit- .ish Patent No. 26,317 .of 1907). Nevertheless, the general fact remains that orthocrescl and para-cresol, in thosereactions which yield infusible condensation products, act more slowly than meta-cresol or phenol.

According to the present inyention this property of orthoand para-cresols is utilized for retarding to any desired degree the moment of final hardening in any of the molding or other processes in which these condensation products have found their industrial uses, and for increasing the thermoplastic quality of the products. In this connection it is explained that orthoand paracresol, and the resinous condensation products derived therefrom, are unusually ood solvents for similar condensation pro 'ucts prepared from meta-cresol or phenol, or

mixtures thereof. There are relatively few substances which can performthe functions of-solid solventsfor the final product after complete final hardening has set in. Most other solvents act as such to a limited extent, or during the preliminary phases of the reaction; but most of them are either partially or totally expelled when complete phenol used for the manufacture ofcondensation products; or b introducing into molding mixtures or 0t er preparations in which phenolic condensation roducts are used, a certain proportion of imtial 'or' inter mediate condensation products prepared;

fusible condensation product in a second step, and so carrying outthis two-step reaction that at first a certain proportion of' special saliretin, pre ared from ortho-cresol or para-cresol or rom mixtures rich in orthoand para-eresol, is added to the saliretin derived from meta-cresohphnol, or mixtures rich in these bodies, or other suitable phenolic bodies. In this way the reaction of the formaldehyde, araform, hexamethylenetetramine, or the like upon the saliretin will be decidedly retarded, allowing at the same time greater plasticity and more latitude in the working of the products. g 4

In fact if para-cresol is' used alone, or is largely' reponderant over the other-phenolic b0 ies, it is possible even when using a large excess of formalde yde or its equiva lents (paraform, hexamethyleneltetramine, etc.) to obtain a final product, infusi'bleat 100 0., which although very hard and strong, yet softens materially at high temperatures (for example 212 (1.), to' the extent of begi to melt or becomi VISCO'US; or the r not may beso prepa that it is decid edly fusible [at these h temperatures or at temperatures'materia y above 115 for instance by ,the use of cresol in higher proportions. .As'an ex ample, a hard, tough roduct is obtained by heatin 100 parts y weight of. acresol wit 45 parts by weight orient;- methylenetetramme, 4 either in presence (or absence of water, in anopen vessel at about ISO-200 C. until a portion"only of the ammonia has been driven ofi;*then cooling somewhat and pouring the yet, liquid mass lnto a container; andthereafter hardening used by heating for about twenty-four hours at a out 165 0,, this heating'being preferably .carrled out under increased ressure, as

the operation is otherwise di cult trite);-

trol and is apt to reduce irre The proportion oi hexamethy enetetramine may be varied considerabl for ex;- ample, quite similar results areio by using in the above example either thn'ty grams of hexamethglenetetramine, orfifty grams. Instead of examethylenetetramine a mixture of formaldehyde and'ammonia can be used. which is equivalent in its action,

s'ation' -prodi1'cts".0f the'i iinfusible 't f'rodu includingthe crab nnwo hdarst ane t become infusible It should centred that phenol and metacresol, under 'conditions as specified above,-

yield mfusible products.

The product from para-cresol, although fusible, is decidedly less so than ordinary saliretih resins, which melt at temperatures in the neighborhood of 100 (1., or even lower thanthis; B diminishingthe-prortion, of hexametiiylenetetramlne or of ormaldehyde, yet more fusible products are obtained, but they are also more brittle. *Inwiew of the dliferences as above set forthin the properties of condensation products'derived' from phenol and from the isomeric cresol's, it will beseen that orthoereso'l and para-cresol,'fas well as "mixtures 'thereofiareto be regarded for the purposes of this invention as" equivalent plasticiting Yand retarding it cuts for-condensatio'n products prepare Tfrom, meta-cresol or' mixtures thereof,

{As stated above" I'have found it possible under proper conditions-to prepare conde'n e from drthacresol, ineludingi'nixtnres su cien'tly enriched inorthomresol. Following-are oerphenol or yielding-inflexible t4; or a 40 ercent formaldeh de solution and 1i6'cub1c-fcentiineters of strong agiieoushydrochlorid acidt '-"lhe'-' ueoiis la'yeris' boiled Haas-to riepreem s a fusible mainertpe-salirain pounds; fraeprcaea'a 1 I I fuisible.

and

150 grains bit-40' cent formaldehyde; in presences: 2.5 cu icceiitiineterspf strong aqueous hydrochloric acid; ,"The miracle is boiled .for' *rninut'e's', and" the reaction product "heatedunder sixty? pounds steam re d n tain typical examples of operating methods es-evapg aaa d 1 100 grams tr mmers-01am mixed with ousse ten to fourteen hours. The product is infusible, tough and hard.

Example 'I V.

100 grams ortho-cresol are mixed with eighty grams of formaldehyde and five grams of caustic soda. The mixture is boiled one-half hour, and the resulting roduot heated under pressure as above.

he product is very hard, tough and infusible. A similar product was obtained using 100 grams of ortho-cresol, 100 grams of formaldeh de solution, and three grams of caustic soda. Caustic potash is equivalent to caustic soda in this reaction.

Under proper conditions ortho-cresol may be made to yield a condensation product which while tough and horny is nevertheless fusible.

Example V.

100 grams ortho-c'resol are mixed with forty grams of hexamethylenetetramine and heated to 200 C., then in a closed vessel for 24 hours under ninety pounds steam pressure. The roduct was tough, with a horny cut but stifi fusible.

'fhe present a plication is a continuation of m prior app lcation Serial No. 130,432, filed ovember Q, 1916.

portion existing in condensation products derived from commercial cresol mixtures, and by the presence therein of ammonia.

3. In a process of making phenolic condensation products, the step which consists in reacting with a body containing a mobile .methylene group upon a phenolic mixture enriched in ortho-cresol.

4. In a process of making phenolic condensation products, the step which consists in reacting with a body containing a mobile vmethylene group upona cresol mixture enriched in ortho-cresol.

In testimony whereof, I afiix my signature.

LEO H. BAEKELAND. 

